全文获取类型
收费全文 | 1826篇 |
免费 | 53篇 |
国内免费 | 8篇 |
专业分类
化学 | 1482篇 |
晶体学 | 31篇 |
力学 | 27篇 |
数学 | 60篇 |
物理学 | 287篇 |
出版年
2023年 | 8篇 |
2022年 | 18篇 |
2021年 | 15篇 |
2020年 | 24篇 |
2019年 | 25篇 |
2018年 | 17篇 |
2016年 | 30篇 |
2015年 | 31篇 |
2014年 | 39篇 |
2013年 | 112篇 |
2012年 | 87篇 |
2011年 | 97篇 |
2010年 | 73篇 |
2009年 | 67篇 |
2008年 | 112篇 |
2007年 | 86篇 |
2006年 | 108篇 |
2005年 | 96篇 |
2004年 | 80篇 |
2003年 | 81篇 |
2002年 | 107篇 |
2001年 | 30篇 |
2000年 | 21篇 |
1999年 | 31篇 |
1998年 | 16篇 |
1997年 | 24篇 |
1996年 | 26篇 |
1995年 | 21篇 |
1994年 | 18篇 |
1993年 | 20篇 |
1992年 | 17篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 10篇 |
1987年 | 10篇 |
1986年 | 12篇 |
1985年 | 36篇 |
1984年 | 25篇 |
1983年 | 14篇 |
1982年 | 28篇 |
1981年 | 20篇 |
1980年 | 27篇 |
1979年 | 22篇 |
1978年 | 17篇 |
1977年 | 16篇 |
1976年 | 17篇 |
1975年 | 15篇 |
1973年 | 12篇 |
1972年 | 8篇 |
排序方式: 共有1887条查询结果,搜索用时 15 毫秒
31.
[reaction: see text] Highly basic lithium enolates are shown to be applicable to radical trifluoromethylation. The reaction is extremely fast, and the minimum reaction time is approximately 1 s. 相似文献
32.
Yoichiro Iwase Koichi Kondo Kenji Kamada Koji Ohta 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3534-3541
1,4‐Bis(4‐benzylpyridinium)butadiyne triflate was aggregated in dimethylformamide and spontaneously converted into the 1,4‐addition type of polydiacetylene. The polymerization took place in a dipolar aprotic solvent with a large dielectric constant that could enhance the aggregation of the ionic diacetylene salt through the electrostatic interaction. The molecular weight of the diacetylene was leveled off after 30 h at 80 °C to reach 1.5 × 104 (number‐average molecular weight) that consisted of the 1,4‐addition type of polydiacetylene similar to polydiacetylenes obtained in the conventional solid‐state polymerization. Electron spin resonance spectra revealed that diradicals were generated at the earlier state aggregation to give rise to a solution polymerization. The UV spectra also suggested the presence of the activated aggregation associated with the polymerization as well as the eximer emission spectra. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3534–3541, 2002 相似文献
33.
Tamás Veszprémi Yoshiya Harada Koichi Ohno Hideki Mutoh 《Journal of organometallic chemistry》1983,252(2):121-125
Penning ionization electron spectroscopy and CNDO/S calculations have been successfully applied to the analyses of the UV photoelectron spectra of 2- and 2,5-bistrimethylsilylthiophene and 2-t-butylthiophene. The relative intensities of the π type bands are greatly enhanced in the Penning spectra compared with those of the UV photoelectron spectra. 相似文献
34.
Hong-Ling Li Koichi Takahashi Yusuke Ujihira Mariko Ishiwatari Kurima Kobayashi Takahiko Iriyama Tokuzo Konishi 《Journal of Thermal Analysis and Calorimetry》1995,45(6):1359-1371
The Mössbauer spectra of Sm2Fe17Nx, prepared by the nitrogenation of Sm2Fe17 powders in an ammonia and hydrogen atmosphere, were observed at elevated temperatures to shed light on the thermal behavior of nitrogen in the compounds Sm2Fe17Nx. It was found that there were large differences in thermal behavior between the starting Sm2Fe17, crystalline Sm2Fe17Nx (x≈1.7) and amorphous Sm2Fe17Nx(x~7). The thermal decomposition behavior of Sm2Fe17N3.2, developed as one of the most promising hard magnetic materials, was found to be different under different atmospheres. 相似文献
35.
Guan-Wu Wang Ting-Hu ZhangEr-Hong Hao Li-Juan JiaoYasujiro Murata Koichi Komatsu 《Tetrahedron》2003,59(1):55-60
The solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes (RCHO) 2a-e under high-speed vibration milling (HSVM) conditions have been investigated. Fulleropyrrolidines 4a-e (C60(CH2N(CH3)CHR), R=H (4a), C6H5 (4b), p-NO2-C6H4 (4c), p-CH3O-C6H4 (4d), p-(CH3)2N-C6H4 (4e)) were obtained in moderate yields from reactions of C60 with aldehydes 2a-e and N-methylglycine (Prato reaction). In all these solvent-free reactions, 4a was found to be formed besides 4b-e, indicating that fullerenes can react with N-substituted glycines in the absence of aldehyde to give fulleropyrrolidines. For this novel reaction, a possible reaction mechanism involving an electron transfer process has been proposed. Intrigued by this observation, the dependence of the yield on the reagent ratio for the reaction of C60 with paraformaldehyde and/or N-methylglycine was examined to search the optimal conditions. The reaction of C70 with paraformaldehyde and/or N-methylglycine under HSVM conditions was also studied and was found to give the positional isomers of [70]fulleropyrrolidines. 相似文献
36.
Koichi Tokuda Tatsuro Gueshi Hiroaki Matsuda 《Journal of Electroanalytical Chemistry》1979,102(1):41-48
Faradaic, impedances at model electrodes partially covered with a photoresist layer have been studied theoretically and experimentally. Equations for the faradaic impedance are derived based on the theoretical model and approach described in Part I of this series of papers. Experimental data for the hexacyanoferrate system at various model electrodes give excellent agreement, with theoretical predictions for the diffusion impedance behavior, and the applicability of the derived equations to the estimation of the degree of coverage and the size of the active regions is confirmed. Furthermore, the application of such model electrodes to the kinetic study of electrode reactions with high heterogeneous charge transfer rates is suggested. 相似文献
37.
The infrared spectra of the carbon monoxide-water cluster as well as the CO monomer and dimer in an argon matrix at cryogenic temperatures have been reinvestigated on the basis of the isotope substitution experiment with 12CO and 13CO. Lines due to the CO-H2O 2-1 cluster in the matrix have been unambiguously identified in the CO and OH stretching regions. The isotope effect on the vibrational frequency of the cluster is observed in the CO stretching vibration but neither in the symmetric nor antisymmetric OH stretching vibrations. Each of the two vibrational lines due to the two CO vibrations of the CO-H2O 2-1 cluster is examined by comparing the expected spectral features at a 12CO/13CO ratio on a simulation with those observed experimentally. The migration of the trapped molecules (CO and H2O) in the matrix is discussed, in which the observed spectral change with the deposition temperature from 14 K to 30 K is explained. 相似文献
38.
Yasushi Joh Koichi Harada Heimei Yuki Shunsuke Murahashi 《Journal of polymer science. Part A, Polymer chemistry》1971,9(4):1089-1102
The polymerization of isobutyl vinyl ether by vanadium trichloride in n-heptane was studied. VCl3 ? LiCl was prepared by the reduction of VCl4 with stoichiometric amounts of BuLi. This type of catalyst induces stereospecific polymerization of isobutyl vinyl ether without the action of trialkyl aluminum to an isotactic polymer when a rise in temperature during the polymerization was depressed by cooling. It is suggested that the cause of the stereospecific polymerization might be due to the catalyst structure in which LiCl coexists with VCl3, namely, VCl3 ? LiCl or VCl2 ? 2LiCl as a solid solution in the crystalline lattice, since VCl3 prepared by thermal decomposition of VCl4 and a commercial VCl3 did not produce the crystalline polymer and soluble catalysts such as VCl4 in heptane and VCl3 ? LiCl in ether solution did not yield the stereospecific polymer. It was found that some additives, such as tetrahydrofuran or ethylene glycol diphenyl ether, to the catalyst increased the stereospecific polymerization activity of the catalysts. Influence of the polymerization conditions such as temperature, time, monomer and catalyst concentrations, and the kind of solvent on the formed polymer was also examined. 相似文献
39.
There have been many experimental and theoretical studies on molecular conduction, as it is a fundamental parameter in the study of molecular‐scale electronics. We have investigated the features of molecular conduction using a Green's function method, which has often been used to solve problems in quantum transport and is also effective in elucidating electron transport in molecules. We have obtained the novel effective Green's functions, including the first‐order energy corrections, by accommodating the self‐energy of the electrodes as perturbation terms. Although these approximate Green's functions only provide information on the first‐order energy corrections, they can involve the elementary properties of molecular conduction. We propose a scheme for the analysis of the relations between molecular orbitals and their roles in molecular conduction and present analytical calculations for normal and cyclic polyenes. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
40.
Horio T Yamazaki M Maeda S Hatamoto T Kishimoto N Ohno K 《The Journal of chemical physics》2005,123(19):194308
A low-temperature discharge nozzle source with a liquid-N(2) circulator for He*(2(3)S) metastable atoms has been developed in order to obtain the state-resolved collision energy dependence of Penning ionization cross sections in a low collision energy range from 20 to 80 meV. By controlling the discharge condition, we have made it possible to measure the collision energy dependence of partial ionization cross sections (CEDPICS) for a well-studied system of CH(3)CN+He*(2(3)S) in a wide energy range from 20 to 350 meV. The anisotropic interaction potential energy surface for the present system was obtained starting from an ab initio model potential via an optimization procedure based on classical trajectory calculations for the observed CEDPICS. A dominant attractive well depth was found to be 423 meV (ca. 10 kcal/mol) at a distance of 3.20 A from the center of mass of CH(3)CN in the N-atom side along the CCN axis. In addition, a weak attractive well (ca. 0.9 kcal/mol) surrounding the methyl group (-CH(3)) has been found and ascribed to the interaction between an unoccupied molecular orbital of CH(3)CN and 2s atomic orbital of He*(2(3)S). 相似文献